CN1796438A - Nylon possessing favorable spinning quality, and preparation method - Google Patents
Nylon possessing favorable spinning quality, and preparation method Download PDFInfo
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- CN1796438A CN1796438A CN 200410099224 CN200410099224A CN1796438A CN 1796438 A CN1796438 A CN 1796438A CN 200410099224 CN200410099224 CN 200410099224 CN 200410099224 A CN200410099224 A CN 200410099224A CN 1796438 A CN1796438 A CN 1796438A
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Abstract
This invention relates to a nylon product with good spinning properties and its preparation method. This nylon product is solution-polymerized from matrix nylon monomers with the addition of long-chain nylon and its salts, and the mass ratio between matrix nylon monomers, long-chain nylon and long-chain nylon salts is (60~98): (6~40): (1~10). Due to good elongation rate and melting index, the nylon product in this invention is extremely eligible for spinning. Even in common spinning conditions, fine denier and ultra-fine denier filaments can be prepared from this nylon product.
Description
Technical field
The present invention relates to a kind of method of improving the nylon spinning properties, particularly common nylon is carried out that modification improves its unit elongation and the method for improving spinning properties.
Background technology
Because the nylon fiber fabric has absorbing sweat, lightweight, characteristics such as snappiness is good, rebound resilience good, antiacid alkali, is best suited for one of man-made fabric of human dress.Application on clothes also is one of main application of nylon fiber, and nylon fiber is thin more, and the snugness of fit of its fabric is high more.Along with growth in the living standard, garment material mainly is to use fine denier filament and superfine denier fiber now.Can spin fine denier filament and superfine denier fiber by the improvement to conventional spinning process, its innovative approach mainly contains: 1. reduce the aperture of spinning jet, and as using the 0.2mm even the spinning jet of fine pore more, and the hole count of corresponding increase spinning jet; 2. filter to improve the purity of spinning melt by high precision; 3. reduce the level of stretch and the degree of molecular orientation of spray silk tow to the winding process, to keep the extension ability of tow more; 4. take higher drafting multiple.
Require in the improved spinning process that the spinning material melt viscosity is low, breaking elongation will be got well.Low melt viscosity helps to reduce spinning pressure, enhances productivity; Good breaking elongation performance can obtain higher drafting multiple.But because spinning technique reduce melt viscosity and realize by the molecular weight that reduces nylon usually, and this can damage the breaking elongation performance of nylon.Increasing substantially the breaking elongation performance of nylon by modification, reduce the viscosity of nylon on this basis again, obtain to take into account the nylon raw material of breaking elongation performance and melt viscosity, is the feasible way that addresses this problem.
According to literature survey, improving the work carried out aspect the common nylon spinning property and few by modification, mainly be by copolymerization or add auxiliary agent and reduce the molecular orientation of common nylon when reeling, extend ability to improve monofilament.Mainly contain: introduce asymmetric cell by copolymerization, to reduce the ability of molecular orientation.Mainly be hexanolactam and the assorted hexane of azo-cycle that when common nylon polymerization, adds asymmetric diprotic acid, diamine or band side group;
Add acrylic acid derivative when spinning, as methyl methacrylate, can reduce the alignment capability of common nylon molecule effectively, concrete mechanism is unclear.
Aforesaid method can only be conceived to by copolymerization or add auxiliary agent and reduce the molecular orientation ability of common nylon, and does not consider to improve by modification the breaking elongation of common nylon.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of nylon with favorable spinning quality and preparation method thereof for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of nylon with favorable spinning quality, it is characterized in that, this nylon is to have added long-chain nylon and salt thereof when the monomer polymerization of matrix nylon, and the weight ratio of described matrix nylon monomer, long-chain nylon, long-chain nylon salt is 60～98: 6～40: 1～10.
Described matrix nylon is to be formed by cyclic lactames monomer or its corresponding amino acid homopolymerization or copolymerization, and described cyclic lactames has structure shown in the formula (I), and its corresponding amino acid has structure shown in the formula (I '):
Among formula (I), (I '), A is H or the alkyl with 1-8 carbon atom, 3≤n≤11.
Described cyclic lactames monomer is to be selected from the following monomer one or more: butyrolactam, Valerolactim, hexanolactam, oenantholactam, spicy inner formyl amine, the ninth of the ten Heavenly Stems lactan, caprinolactam, 11 lactan, laurolactam, N-methyl caprolactam, N-n-octyl lactan in the ninth of the ten Heavenly Stems, N-tertiary butyl laurolactam; Corresponding amino acid comprises that omega-amino-butyric acid, omega-amino-valeric acid, omega-amino-caproic acid, omega-amino-enanthic acid, omega-amino-are sad, omega-amino-n-nonanoic acid, omega-amino-capric acid, omega-amino-undeeanoic acid, omega-amino-laurostearic acid.
The molecular weight of described matrix nylon is between 10,000 to 20,000.
Described long-chain nylon is meant in the repeating unit that carbonatoms on the main chain is at least 8 nylon, and these nylon comprise that repeating unit is suc as formula (II), (III) with the nylon (IV):
(-NH-D-NH-CO-E-CO-)
p (II)
In the formula (II), D represents-(CH
2)
x-, H wherein can be randomly by C
1-4Alkyl replaces; E represents-(CH
2)
y-or phenylene, H wherein can be randomly by C
1-4Alkyl replaces; 4≤x≤34; 4≤y≤34;
(-NH-(CH
2)
w-CO-)
p (III)
In the formula (III), 7≤w≤34;
(-NH-(CH
2)
u-CO-NH-(CH
2)
v-CO-)
p (IV)
In the formula (IV), 5≤u≤34,5≤v≤34, and u ≠ v.
Described long-chain nylon is selected from nylon-1010, nylon-11 11, PA-12 12, nylon-1313, nylon-46, nylon-610, nylon-6 12, nylon-6 13, nylon-10 11, nylon-10 12, PA-12 13, it is poly-that (paraphenylene terephthalamide 2,2,4-trimethylammonium hexanediamine), poly-(3-tertiary butyl hexanedioyl heptamethylene diamine), nylon-8, nylon-9, nylon-11, PA-12, nylon-13, copolycondensation nylon 6/10, copolycondensation nylon 6/12, copolycondensation nylon 6/13, copolycondensation nylon 10/11, copolycondensation nylon 10/12, copolycondensation nylon 12/13, nylon 10T, and their combination; There is no particular restriction for the molecular weight of long-chain nylon, as long as can be dissolved in cyclic lactames or its corresponding amino acid.
Described long-chain nylon salt is meant the nylon salt that can aggregate into long-chain nylon.
A kind of preparation method with nylon of favorable spinning quality, it is characterized in that, this method comprises following processing step: long-chain nylon and long-chain nylon salt are dissolved in lactam monomers or its corresponding amino acid, lactam monomers or its corresponding amino acid are carried out polyreaction, described dissolving step and polymerization procedure are carried out simultaneously, perhaps dissolve earlier the solution that obtains is carried out polymerization, the weight ratio of described lactam monomers or its corresponding amino acid, long-chain nylon, long-chain nylon salt is 60～98: 6～40: 1～10.
Described polyreaction is to adopt hydrolytic polymerization technology to carry out, this hydrolytic polymerization technology may further comprise the steps: add long-chain nylon and long-chain nylon salt in cyclic lactames monomer or its corresponding amino acid, heating for dissolving, add entry, in temperature is that 200～250 ℃, pressure are the polymerization that is hydrolyzed under the condition of 0.1～20MPa, 0.5 decompression and vacuum hydro-extraction after～6 hours continue polymerization with further raising viscosity, make the nylon with favorable spinning quality.
The invention provides a kind of method that can improve common nylon spinning properties.This method is to add long carbon chain nylon and salt thereof in the polymerization of spinning matrix nylon, in spinning matrix nylon, introduce the long carbon chain nylon segment, can effectively reduce the probability of amide group Cheng Jian, thereby reduce the molecular orientation ability of spinning matrix nylon, increase the toughness of matrix nylon simultaneously, improved the tension set of matrix nylon.Matrix nylon is used for the molecular weight of spinning greatly between 10,000 to 20,000.With nylon 6 is example, its melting index is at 230 ℃, 2.16Kg pressure be down 20-30g/min, tension set is about 160%, and after adding the long-chain nylon modification, (melting index is 40～50g/min) under the pressure of 2.16Kg at 230 ℃, and tension set is brought up to 400%-500% by 160% under the situation that reduces melt viscosity.The nylon of this modification extremely is fit to spinning fine denier filament and superfine denier fiber.Under common spinning technique, can spin the fine denier filament that fiber number is 1-5dtex.
The present invention adopts the matrix nylon of long-chain nylon to cyclic lactames or amino acid homopolymerization or copolymerization formation, obtains high-elongation nylon.Tensile strength, elongation at break that this nylon tool is good.In addition, also have extraordinary resistance to low temperature, also reduce not quite-40 ℃ of its toughness.Because long-chain nylon can be dissolved in the lactam monomers, so the inventive method is simple and easy to operate.
Because the nylon material that the inventive method makes has good unit elongation and melting index, therefore be very suitable for spinning, under common spinning technique, adopt the nylon material of the inventive method preparation also can prepare thin dawn or superfine denier fiber.
The nylon material that the present invention makes can carry out spinning under common spinning technique: nozzle plate bore dia 1mm, curled hair speed 40m/s, spinning pressure 28MPa, 5 times of drawing-offs.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and in an embodiment, each components contents is weight part.
Embodiment 1
In 90 parts of caprolactam monomers, add 10 parts of nylon-10 12 resins, 140 ℃ of dissolvings down.Add 9 parts of deionized waters again, be pressurized to 1MPa, and be warmed up to 230 ℃, hydrolytic polymerization 4 hours.Reduce pressure then and vacuumize and continued polymerization 2 hours, spinning is carried out in the inflated with nitrogen discharging, the nozzle plate aperture 1mm of employing, and spinning pressure 28MPa can spin the silk at 1 dawn.
Embodiment 2
Section and 3 part of 13 lactan of adding 40 parts of nylon 13 in 60 parts of caprolactam monomers are 140 ℃ of dissolvings down.Add 25 parts of deionized waters, be warmed up to 250 ℃ and be pressurized to the 2MPa hydrolytic polymerization, after half an hour, reduce pressure and vacuumize and remove moisture content, continue polymerization with further raising viscosity, after 6 hours, spinning is carried out in discharging, the nozzle plate aperture 1mm that adopts, spinning pressure 28MPa can spin the silk at 1.5 dawn.
Embodiment 3
In 90 parts of N-methyl caprolactam monomers, add 10 parts of nylon-10 12 resins and 4 portions of nylon 1012 salt, 140 ℃ of dissolvings down.Add 25 parts of deionized waters again, be pressurized to 1.2MPa, and be warmed up to 230 ℃, hydrolytic polymerization 4 hours.Reduce pressure then and vacuumize and continued polymerization 2 hours, spinning is carried out in the inflated with nitrogen discharging, the nozzle plate aperture 1mm of employing, and spinning pressure 28MPa can spin the silk at 1.5 dawn.
Embodiment 4
The section that adds 35 parts of nylon 13 in 65 parts of N-n-octyl lactam monomers in the ninth of the ten Heavenly Stems is 140 ℃ of dissolvings down.Add 25 parts of deionized waters, be warmed up to 250 ℃ and be pressurized to the 2MPa hydrolytic polymerization, after half an hour, reduce pressure and vacuumize and remove moisture content, continue polymerization with further raising viscosity, after 6 hours, the pressurization discharging is carried out spinning, the nozzle plate aperture 1mm of employing, spinning pressure 28MPa can spin the silk at 2 dawn.
Embodiment 5
The 2 portions of nylon 1212 salt of section that add 28 parts of nylon nylon 1212s in 70 parts of caprinolactam monomers are 140 ℃ of dissolvings down.Add 70 parts of deionized waters, be warmed up to 200 ℃ and be pressurized to the 10MPa hydrolytic polymerization, after 6 hours, reduce pressure and vacuumize and remove moisture content, continue polymerization with further raising viscosity, after 0.2 hour, spinning is carried out in the pressurization discharging, the nozzle plate aperture 1mm that adopts, spinning pressure 28MPa can spin the silk at 1 dawn.
Embodiment 6
In 90 parts of N-methyl caprolactam monomers, add 10 parts of nylon-10s 12 and 9 parts of deionized waters, be pressurized to 1.2MPa, and be warmed up to 230 ℃, hydrolytic polymerization 4 hours.Reduce pressure then and vacuumize and continued polymerization 2 hours, spinning is carried out in the inflated with nitrogen discharging, the nozzle plate aperture 1mm of employing, and spinning pressure 28MPa can spin the silk at 1 dawn.
Claims (9)
1. nylon with favorable spinning quality, it is characterized in that, this nylon is to have added long-chain nylon and salt thereof when the monomer polymerization of matrix nylon, and the weight ratio of described matrix nylon monomer, long-chain nylon, long-chain nylon salt is 60～98: 6～40: 1～10.
2. a kind of nylon according to claim 1 with favorable spinning quality, it is characterized in that, described matrix nylon is to be formed by cyclic lactames monomer or its corresponding amino acid homopolymerization or copolymerization, described cyclic lactames has structure shown in the formula (I), and its corresponding amino acid has structure shown in the formula (I '):
Among formula (I), (I '), A is H or the alkyl with 1-8 carbon atom, 3≤n≤11.
3. a kind of nylon according to claim 2 with favorable spinning quality, it is characterized in that described cyclic lactames monomer is to be selected from the following monomer one or more: butyrolactam, Valerolactim, hexanolactam, oenantholactam, spicy inner formyl amine, the ninth of the ten Heavenly Stems lactan, caprinolactam, 11 lactan, laurolactam, N-methyl caprolactam, N-n-octyl lactan in the ninth of the ten Heavenly Stems, N-tertiary butyl laurolactam; Corresponding amino acid comprises that omega-amino-butyric acid, omega-amino-valeric acid, omega-amino-caproic acid, omega-amino-enanthic acid, omega-amino-are sad, omega-amino-n-nonanoic acid, omega-amino-capric acid, omega-amino-undeeanoic acid, omega-amino-laurostearic acid.
4. a kind of nylon with favorable spinning quality according to claim 1 is characterized in that the molecular weight of described matrix nylon is between 10,000 to 20,000.
5. a kind of nylon according to claim 1 with favorable spinning quality, it is characterized in that, described long-chain nylon is meant in the repeating unit that carbonatoms on the main chain is at least 8 nylon, and these nylon comprise that repeating unit is suc as formula (II), (III) with the nylon (IV):
(-NH-D-NH-CO-E-CO-)
p (II)
In the formula (II), D represents-(CH
2)
x-, H wherein can be randomly by C
1-4Alkyl replaces; E represents-(CH
2)
y-or phenylene, H wherein can be randomly by C
1-4Alkyl replaces; 4≤x≤34; 4≤y≤34;
(-NH-(CH
2)
w-CO-)
p (III)
In the formula (III), 7≤w≤34;
(-NH-(CH
2)
u-CO-NH-(CH
2)
v-CO-)
p (IV)
In the formula (IV), 5≤u≤34,5≤v≤34, and u ≠ v.
6. a kind of nylon according to claim 5 with favorable spinning quality, it is characterized in that, described long-chain nylon is selected from nylon-1010, nylon-11 11, PA-12 12, nylon-1313, nylon-46, nylon-610, nylon-6 12, nylon-6 13, nylon-10 11, nylon-10 12, PA-12 13, it is poly-that (paraphenylene terephthalamide 2,2,4-trimethylammonium hexanediamine), poly-(3-tertiary butyl hexanedioyl heptamethylene diamine), nylon-8, nylon-9, nylon-11, PA-12, nylon-13, copolycondensation nylon 6/10, copolycondensation nylon 6/12, copolycondensation nylon 6/13, copolycondensation nylon 10/11, copolycondensation nylon 10/12, copolycondensation nylon 12/13, nylon 10T, and their combination; There is no particular restriction for the molecular weight of long-chain nylon, as long as can be dissolved in cyclic lactames or its corresponding amino acid.
7. a kind of nylon with favorable spinning quality according to claim 1 is characterized in that described long-chain nylon salt is meant the nylon salt that can aggregate into long-chain nylon.
8. preparation method with nylon of favorable spinning quality, it is characterized in that, this method comprises following processing step: long-chain nylon and long-chain nylon salt are dissolved in lactam monomers or its corresponding amino acid, lactam monomers or its corresponding amino acid are carried out polyreaction, described dissolving step and polymerization procedure are carried out simultaneously, perhaps dissolve earlier the solution that obtains is carried out polymerization, the weight ratio of described lactam monomers or its corresponding amino acid, long-chain nylon, long-chain nylon salt is 60～98: 6～40: 1～10.
9. a kind of preparation method according to claim 8 with nylon of favorable spinning quality, it is characterized in that, described polyreaction is to adopt hydrolytic polymerization technology to carry out, this hydrolytic polymerization technology may further comprise the steps: add long-chain nylon and long-chain nylon salt in cyclic lactames monomer or its corresponding amino acid, heating for dissolving, add entry, in temperature is 200～250 ℃, pressure is the polymerization that is hydrolyzed under the condition of 0.1～20MPa, 0.5 decompression and vacuum hydro-extraction after～6 hours, continue polymerization with further raising viscosity, make nylon with favorable spinning quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410099224 CN1796438A (en) | 2004-12-29 | 2004-12-29 | Nylon possessing favorable spinning quality, and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410099224 CN1796438A (en) | 2004-12-29 | 2004-12-29 | Nylon possessing favorable spinning quality, and preparation method |
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| CN1796438A true CN1796438A (en) | 2006-07-05 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108385203A (en) * | 2018-02-12 | 2018-08-10 | 广东新会美达锦纶股份有限公司 | A kind of preparation method of resistance to discoloration antibacterial nylon fiber |
| CN111809271A (en) * | 2020-07-06 | 2020-10-23 | 御澜星新能源科技(江苏)有限公司 | High-performance nano ceramic uvioresistant high-thermal insulation fiber and preparation method thereof |
| CN116515103A (en) * | 2022-01-24 | 2023-08-01 | 成都肆零壹科技有限公司 | Low-water-absorption high-temperature-resistant copolymerized nylon and preparation method thereof |
-
2004
- 2004-12-29 CN CN 200410099224 patent/CN1796438A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108385203A (en) * | 2018-02-12 | 2018-08-10 | 广东新会美达锦纶股份有限公司 | A kind of preparation method of resistance to discoloration antibacterial nylon fiber |
| CN108385203B (en) * | 2018-02-12 | 2021-01-26 | 广东新会美达锦纶股份有限公司 | Preparation method of discoloration-resistant antibacterial polyamide fiber |
| CN111809271A (en) * | 2020-07-06 | 2020-10-23 | 御澜星新能源科技(江苏)有限公司 | High-performance nano ceramic uvioresistant high-thermal insulation fiber and preparation method thereof |
| CN116515103A (en) * | 2022-01-24 | 2023-08-01 | 成都肆零壹科技有限公司 | Low-water-absorption high-temperature-resistant copolymerized nylon and preparation method thereof |
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Open date: 20060705 |